CN110697793B - Two-dimensional transition metal chalcogenide and preparation method and application thereof - Google Patents
Two-dimensional transition metal chalcogenide and preparation method and application thereof Download PDFInfo
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- -1 transition metal chalcogenide Chemical class 0.000 title claims abstract description 63
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 102
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims abstract description 96
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000000243 solution Substances 0.000 claims abstract description 57
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 48
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 48
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 48
- 239000002135 nanosheet Substances 0.000 claims abstract description 46
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 43
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 43
- 239000012266 salt solution Substances 0.000 claims abstract description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 35
- UOJLTGJDEASXFF-UHFFFAOYSA-N [Mn].[Co].[Fe] Chemical compound [Mn].[Co].[Fe] UOJLTGJDEASXFF-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000002156 mixing Methods 0.000 claims abstract description 35
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000012670 alkaline solution Substances 0.000 claims abstract description 19
- 238000000975 co-precipitation Methods 0.000 claims abstract description 15
- 238000006073 displacement reaction Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 4
- 239000010941 cobalt Substances 0.000 claims abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 150000002696 manganese Chemical class 0.000 claims description 10
- 238000003384 imaging method Methods 0.000 claims description 9
- 150000001868 cobalt Chemical class 0.000 claims description 8
- 239000002872 contrast media Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000002405 nuclear magnetic resonance imaging agent Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 3
- 229910001437 manganese ion Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- 239000011572 manganese Substances 0.000 abstract description 33
- 239000002243 precursor Substances 0.000 abstract description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000470 constituent Substances 0.000 abstract description 2
- 230000002255 enzymatic effect Effects 0.000 abstract description 2
- 229910052748 manganese Inorganic materials 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 238000005406 washing Methods 0.000 description 27
- 239000008367 deionised water Substances 0.000 description 25
- 229910021641 deionized water Inorganic materials 0.000 description 25
- 238000003756 stirring Methods 0.000 description 18
- 239000006185 dispersion Substances 0.000 description 16
- 210000004027 cell Anatomy 0.000 description 12
- 238000005119 centrifugation Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 9
- 229910021642 ultra pure water Inorganic materials 0.000 description 9
- 239000012498 ultrapure water Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000004083 survival effect Effects 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 6
- 206010028980 Neoplasm Diseases 0.000 description 6
- 150000002505 iron Chemical class 0.000 description 6
- 102000004190 Enzymes Human genes 0.000 description 5
- 108090000790 Enzymes Proteins 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000000502 dialysis Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000007669 thermal treatment Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 230000006907 apoptotic process Effects 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 238000002595 magnetic resonance imaging Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000010186 staining Methods 0.000 description 3
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- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007626 photothermal therapy Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000006144 Dulbecco’s modified Eagle's medium Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000030833 cell death Effects 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
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- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229940124597 therapeutic agent Drugs 0.000 description 1
- 210000004881 tumor cell Anatomy 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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Images
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-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/006—Compounds containing, besides cobalt, two or more other elements, with the exception of oxygen or hydrogen
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/06—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/22—Echographic preparations; Ultrasound imaging preparations ; Optoacoustic imaging preparations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
Abstract
The invention relates to the technical field of preparation of transition metal chalcogenide compounds, in particular to a two-dimensional transition metal chalcogenide compound and a preparation method and application thereof. The invention provides a preparation method of a two-dimensional transition metal chalcogenide, which comprises the following steps: (1) mixing a cobalt-iron-manganese salt solution, a formamide-containing sodium nitrate solution and an alkaline solution, and carrying out coprecipitation to synthesize hydrotalcite nanosheets; (2) and mixing the hydrotalcite nanosheets, thioacetamide and ethanol, and carrying out a displacement reaction to obtain the two-dimensional transition metal chalcogenide. The method takes the hydrotalcite nanosheet as a precursor, is simple in preparation method, and takes the functional metal ions of cobalt, iron and manganese as hydrotalcite layer plate constituent elements, so that the finally prepared two-dimensional transition metal chalcogenide has enzymatic characteristics.
Description
Technical Field
The invention relates to the technical field of preparation of transition metal chalcogenide compounds, in particular to a two-dimensional transition metal chalcogenide compound and a preparation method and application thereof.
Background
The two-dimensional transition metal chalcogenide nanosheet becomes an ideal photo-thermal reagent due to the adjustable band gap, strong spin coupling and high photo-thermal conversion capability. For example, MoS2、WS2、NiTe2And Bi2Se3Have strong optical absorption in the near infrared region, making them useful as photothermal imaging contrast agents and photothermal therapeutic agents. However, the photothermal therapy alone requires laser intensity depending on the depth, and the heat dispersion is not uniform, and the tumor cannot be completely cured.
Disclosure of Invention
The invention aims to provide a two-dimensional transition metal chalcogenide compound and a preparation method and application thereof. The two-dimensional transition metal chalcogenide compound provided by the invention has the characteristics of nano enzyme, overcomes the problems of uneven heat dispersion and the like in single photo-thermal treatment, and realizes the synergistic effect of photo-thermal and catalysis.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a two-dimensional transition metal chalcogenide, which comprises the following steps:
(1) mixing a cobalt-iron-manganese salt solution, a formamide-containing sodium nitrate solution and an alkaline solution, and carrying out coprecipitation to synthesize hydrotalcite nanosheets;
(2) and mixing the hydrotalcite nanosheets, thioacetamide and ethanol, and carrying out a displacement reaction to obtain the two-dimensional transition metal chalcogenide.
Preferably, the cobalt-iron-manganese salt solution in the step (1) is prepared by mixing cobalt salt, iron salt, manganese salt and water, wherein the total concentration of the cobalt salt, the iron salt and the manganese salt in the cobalt-iron-manganese salt solution is 20-40 mmol/L; the molar ratio of cobalt ions, iron ions and manganese ions in the cobalt-iron-manganese salt solution is (1-3): (0.25-0.75): (0.25-0.75).
Preferably, the concentration of formamide in the sodium nitrate solution containing formamide in the step (1) is 4-6 mol/L, and the concentration of sodium nitrate is 9-12 mmol/L; the molar ratio of formamide to sodium nitrate is 400-600: 1.
Preferably, the molar ratio of the sodium nitrate in the formamide-containing sodium nitrate solution in the step (1) to the total amount of the cobalt salt, the iron salt and the manganese salt in the cobalt-iron-manganese salt solution is 1: (2-4).
Preferably, the alkaline solution in step (1) is sodium hydroxide solution, ammonia water or sodium carbonate solution.
Preferably, the mixing manner in step (1) is as follows: dropwise adding the cobalt-iron-manganese salt solution and the alkaline solution into the formamide-containing sodium nitrate solution; the dropping speed of the cobalt-iron-manganese salt solution is 1-3 mu L/s; the dropping speed of the alkaline solution is 1-3 mu L/s.
Preferably, the coprecipitation in the step (1) is carried out under the condition that the pH value is 9-10, and the temperature of the coprecipitation is 75-85 ℃.
Preferably, the temperature of the displacement reaction in the step (2) is 120-150 ℃, and the time of the displacement reaction is 11-13 h.
The invention also provides the two-dimensional transition metal chalcogenide prepared by the preparation method of the technical scheme, which is flaky in appearance and 1.1-1.3 nm in thickness.
The invention also provides application of the two-dimensional transition metal chalcogenide compound in the technical scheme in preparation of a photoacoustic imaging contrast agent or a magnetic resonance imaging contrast agent.
The invention provides a preparation method of a two-dimensional transition metal chalcogenide, which comprises the following steps: (1) mixing a cobalt-iron-manganese salt solution, a formamide-containing sodium nitrate solution and an alkaline solution, and carrying out coprecipitation to synthesize hydrotalcite nanosheets; (2) and mixing the hydrotalcite nanosheets, thioacetamide and ethanol, and carrying out a displacement reaction to obtain the two-dimensional transition metal chalcogenide. The method takes the hydrotalcite nanosheet as a precursor, is simple in preparation method, and takes functional metal ions (cobalt, iron and manganese) as hydrotalcite layer plate constituent elements, so that the finally prepared two-dimensional transition metal chalcogenide has enzymatic characteristics.
The invention also provides the two-dimensional transition metal chalcogenide prepared by the preparation method of the technical scheme, which is flaky in appearance and 1.1-1.3 nm in thickness. The two-dimensional transition metal chalcogenide compound provided by the invention has the characteristics of nano enzyme, overcomes the problems of uneven heat dispersion and the like in single photo-thermal treatment, and realizes the synergistic effect of photo-thermal and catalysis. The example result shows that the two-dimensional transition metal chalcogenide compound provided by the invention has stronger absorption in the near infrared region, and the temperature of 808nm laser irradiation for 10min can be as high as 39.4 ℃; in addition, sulfide has enzyme characteristics, the reaction rate can be promoted by increasing the temperature, in a cell experiment, the survival rate of cancer cells is generally lower than 8% under the concentration of 30 mu g/mL, and the beneficial effects of photo-thermal and catalysis are shown.
The invention also provides application of the two-dimensional transition metal chalcogenide compound in the technical scheme in preparation of a photoacoustic imaging contrast agent or a magnetic resonance imaging contrast agent. The two-dimensional transition metal chalcogenide compound obtained by the method can be used for preparing photoacoustic imaging contrast agents and magnetic resonance imaging contrast agents.
Drawings
FIG. 1 is a TEM image of a two-dimensional transition metal chalcogenide compound obtained in example 4;
FIG. 2 is an AFM image of the two-dimensional transition metal chalcogenide obtained in example 4;
FIG. 3 is a diagram of UV vs. vis of two-dimensional transition metal chalcogenides obtained in examples 1 to 5;
FIG. 4 is a graph showing the temperature change of the two-dimensional transition metal chalcogenide compound obtained in examples 1 to 5 within 10 minutes after 808nm laser irradiation;
FIG. 5 is a diagram showing the catalytic reaction of a two-dimensional transition metal chalcogenide compound obtained in example 4;
FIG. 6 is a graph showing the catalytic reaction of the two-dimensional transition metal chalcogenide obtained in example 4 after heating;
FIG. 7 is a graph of the cell activity of the two-dimensional transition metal chalcogenide-treated HepG2 cells obtained in example 4 after catalytic and catalytic illumination;
FIG. 8 is a PI/CA staining pattern of two-dimensional transition metal chalcogenide treated HepG2 cells obtained in example 4 in the state of cell survival after catalytic and catalytic light irradiation;
FIG. 9 is a MRI image of the two-dimensional transition metal chalcogenide obtained in example 4;
fig. 10 is a photo-acoustic image of the two-dimensional transition metal chalcogenide obtained in example 4.
Detailed Description
The invention provides a preparation method of a two-dimensional transition metal chalcogenide, which comprises the following steps:
(1) mixing a cobalt-iron-manganese salt solution, a formamide-containing sodium nitrate solution and an alkaline solution, and carrying out coprecipitation to synthesize hydrotalcite nanosheets;
(2) and mixing the hydrotalcite nanosheets, thioacetamide and ethanol, and carrying out a displacement reaction to obtain the two-dimensional transition metal chalcogenide.
According to the invention, cobalt-iron-manganese salt solution, formamide-containing sodium nitrate solution and alkaline solution are mixed for coprecipitation to synthesize hydrotalcite nanosheets.
The cobalt-iron-manganese salt solution provided by the invention is preferably prepared by mixing cobalt salt, iron salt, manganese salt and waterAnd synthesizing to obtain the product. In the present invention, the cobalt salt is preferably cobalt nitrate, sulfate or chloride, and in particular embodiments of the present invention, Co (NO) is preferably used3)2·6H2O; the iron salt is preferably ferric nitrate, chloride or sulfate, and in particular embodiments of the invention, Fe (NO) is preferably used3)3·9H2O; the manganese salt is preferably manganese nitrate, chloride or sulphate, and in particular embodiments of the invention, Mn (NO) is preferably used3)2·6H2O; the water is preferably deionized water. In the invention, the total concentration of cobalt salt, iron salt and manganese salt in the cobalt-iron-manganese salt solution is preferably 20-40 mmol/L, and more preferably 30 mmol/L; the molar ratio of cobalt ions, iron ions and manganese ions in the cobalt-iron-manganese salt solution is preferably (1-3): (0.25-0.75): (0.25 to 0.75), more preferably 1:0.25:0.75, 1:0.5:0.5, 1:0.75:0.25, 2:0.25:0.75, 2:0.5:0.5, 2:0.75:0.25, 3:0.25:0.75, 3:0.5:0.5, or 3:0.75: 0.25.
In the invention, the concentration of formamide in the sodium nitrate solution containing formamide is preferably 4-6 mol/L; the concentration of the sodium nitrate is preferably 9-12 mmol/L; the total concentration of the formamide and the sodium nitrate is preferably 5 mol/L; the molar ratio of formamide to sodium nitrate is preferably 400-600: 1, and more preferably 500: 1. In the invention, formamide is used as an organic reagent, after the formamide is added into a system, water molecules in hydrotalcite are quickly replaced by formamide, the interlayer spacing is enlarged to form a swelling phase, under the action of oscillation, mechanical stirring or ultrasound and the like, a transverse sliding force is generated, and a laminated plate is slowly stripped into a single-layer nanosheet; sodium nitrate to provide NO3 -Keeping the plate charge balanced.
In the present invention, the molar ratio of sodium nitrate in the formamide-containing sodium nitrate solution to the total amount of cobalt, iron and manganese salts in the cobalt-iron-manganese salt solution is preferably 1: (2-4), more preferably 1: 3.
In the present invention, the alkaline solution is preferably a sodium hydroxide solution, ammonia water or a sodium carbonate solution; the concentration of the alkaline solution is preferably 0.25 to 0.35mmol/mL, and more preferably 0.3 mmol/mL. The invention provides a necessary alkaline environment for synthesizing the hydrotalcite nano-sheet by using an alkaline solution.
In the invention, the specific mode of mixing the cobalt-iron-manganese salt solution, the formamide-containing sodium nitrate solution and the alkaline solution is preferably as follows: and dropwise adding the cobalt-iron-manganese salt solution and the alkaline solution into the formamide-containing sodium nitrate solution. In the invention, the preferable dropwise addition is that a cobalt-iron-manganese salt solution and an alkaline solution are simultaneously dropwise added into the formamide-containing sodium nitrate solution, so that the addition amount of the cobalt-iron-manganese salt solution and the alkaline solution is basically the same at the same time; the dripping speed is preferably 1-3 mu L/s, and more preferably 2 mu L/s.
In the present invention, the dropwise addition is preferably performed under oil bath stirring conditions; and coprecipitation is carried out in the dripping process to synthesize the hydrotalcite nanosheet. In the invention, the temperature of the coprecipitation is preferably 75-85 ℃, and more preferably 80 ℃; the coprecipitation is preferably carried out under the condition that the pH value is 9-10. The invention adopts oil bath to provide constant temperature for coprecipitation and ensure the stable operation of reaction.
After the coprecipitation is finished, the obtained system is preferably cooled to room temperature, and then is subjected to centrifugation, washing and dialysis in sequence to obtain the hydrotalcite nanosheet. In the present invention, the washing preferably includes ethanol washing and ultrapure water washing performed in this order, the number of times of the ethanol washing is preferably 3 times, and the number of times of the ultrapure water washing is preferably 3 times; the dialysis bag used for dialysis is preferably 3-5 kDa, and more preferably 3 kDa. The invention removes formamide through dialysis, and improves the purity of the product.
In the invention, the hydrotalcite nanosheet is a two-dimensional nanomaterial, and the size of the hydrotalcite nanosheet is preferably 40-80 nm, and more preferably 50-60 nm; the thickness is preferably 1 to 2nm, more preferably 1.1 to 1.2 nm.
After obtaining the hydrotalcite nanosheet, thioacetamide and ethanol are mixed and subjected to a displacement reaction to obtain the two-dimensional transition metal chalcogenide. In the invention, the dosage ratio of the hydrotalcite nano-sheet, thioacetamide and ethanol is preferably (0.3-0.5): (0.6-1): 0.8-1), and more preferably 0.3:0.6: 0.8. In the invention, preferably, the hydrotalcite nanosheets are mixed with part of ethanol to obtain a dispersion of the hydrotalcite nanosheets; mixing thioacetamide with the rest ethanol to obtain an ethanol solution of thioacetamide; and then mixing the dispersion liquid of the hydrotalcite nano-sheets and an ethanol solution of thioacetamide. In the present invention, the volume ratio of the partial ethanol to the remaining ethanol is preferably 1: 1. In the invention, the mixing is preferably carried out under stirring conditions, and the stirring speed is preferably 500-800 r/min, and more preferably 600 r/min.
In the invention, the temperature of the replacement reaction is preferably 110-130 ℃, and more preferably 120 ℃; the time of the replacement reaction is preferably 11-13 h, and more preferably 12 h. The invention replaces part of O in hydrotalcite with S in the same main group through replacement reaction.
After the displacement reaction is finished, the obtained system is preferably cooled to room temperature, and the two-dimensional transition metal chalcogenide is obtained through centrifugation and washing in sequence. In the present invention, the washing preferably includes an ethanol washing and an ultrapure water washing performed in this order, the number of times of the ethanol washing is preferably 3, and the number of times of the ultrapure water washing is preferably 3. The two-dimensional transition metal chalcogenide obtained according to the present invention is preferably brown in color.
The invention also provides the two-dimensional transition metal chalcogenide compound prepared by the preparation method of the technical scheme. The two-dimensional transition metal chalcogenide compound obtained by the invention is flaky, and the thickness is preferably 1.1-1.3 nm, and more preferably 1.1-1.2 nm.
The invention also provides application of the two-dimensional transition metal chalcogenide compound in the technical scheme in serving as a photoacoustic imaging contrast agent or a magnetic resonance imaging contrast agent. The two-dimensional transition metal chalcogenide provided by the invention has the characteristics of nano enzyme, overcomes the problems of uneven heat dispersion and the like in single photo-thermal treatment, realizes the synergistic action of photo-thermal and catalysis, can perform nano catalytic reaction in a tumor area, can generate heat for photo-thermal treatment of tumors after being irradiated by 808nm laser, and can accelerate the nano catalytic reaction; the two-dimensional transition metal chalcogenide provided by the invention can be used for preparing photoacoustic imaging contrast agents and magnetic resonance imaging contrast agents.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
0.20mmol Co (NO)3)2·6H2O、0.15mmolFe(NO3)3·6H2O and 0.05mmol Mn (NO)3)2Dissolving in 10mL of deionized water to obtain a cobalt-iron-manganese salt solution;
dissolving 0.1mmol of sodium nitrate and 50mol of formamide in 10mL of deionized water to obtain a sodium nitrate solution containing formamide;
dissolving 0.0025mol of NaOH in 10mL of deionized water to obtain a sodium hydroxide solution;
simultaneously dropwise adding the cobalt-iron-manganese salt solution and the sodium hydroxide solution into the formamide-containing sodium nitrate solution at the dropwise adding speed of 2 mu L/s, and stirring in an oil bath at the temperature of 80 ℃ until the dropwise adding is finished; naturally cooling the system to room temperature, collecting the obtained sample through centrifugation, respectively washing the sample with ethanol and ultrapure water for three times, and further dialyzing (3kDa) to remove formamide to obtain the hydrotalcite nanosheet;
mixing the obtained 0.4mmol of hydrotalcite nanosheet serving as a precursor with 20mL of ethanol to obtain a dispersion liquid of the hydrotalcite nanosheet; mixing 0.8mmol thioacetamide with 20mL ethanol, and stirring at room temperature for 10min under the condition of 600r/min to obtain an ethanol solution of thioacetamide; then mixing the dispersion liquid of the hydrotalcite nano-sheets with an ethanol solution of thioacetamide, and stirring at the room temperature of 600r/min for 30min to obtain a mixed solution; placing the obtained mixed solution in a high-pressure kettle, heating to 120 ℃, keeping for 12 hours, cooling to room temperature to obtain a sample, and washing with ethanol and deionized water for three times respectively; at the final centrifugation, the brown product is dispersed after washing with ethanolStoring in ionized water at 4 deg.C in refrigerator for later use to obtain brown product as two-dimensional transition metal chalcogenide with chemical formula of Co2Fe0.5Mn1.5S4。
Example 2
0.20mmol Co (NO)3)2·6H2O、0.10mmolFe(NO3)3·6H2O and 0.10mmol Mn (NO)3)2Dissolving in 10mL of deionized water to obtain a cobalt-iron-manganese salt solution;
dissolving 0.1mmol of sodium nitrate and 50mmol of formamide in 10mL of deionized water to obtain a sodium nitrate solution containing formamide;
dissolving 0.0025mol of NaOH in 10mL of deionized water to obtain a sodium hydroxide solution;
simultaneously dropwise adding the cobalt-iron-manganese salt solution and the sodium hydroxide solution into the formamide-containing sodium nitrate solution at the dropwise adding speed of 2 mu L/s, and stirring in an oil bath at the temperature of 80 ℃ until the dropwise adding is finished; naturally cooling the system to room temperature, collecting the obtained sample through centrifugation, respectively washing the sample with ethanol and ultrapure water for three times, and further dialyzing (3kDa) to remove formamide to obtain the hydrotalcite nanosheet;
mixing the obtained 0.4mmol of hydrotalcite nanosheet serving as a precursor with 20mL of ethanol to obtain a dispersion liquid of the hydrotalcite nanosheet; mixing 0.8mmol thioacetamide with 20mL ethanol, and stirring at room temperature for 10min under the condition of 600r/min to obtain an ethanol solution of thioacetamide; then mixing the dispersion liquid of the hydrotalcite nano-sheets with an ethanol solution of thioacetamide, and stirring at the room temperature of 600r/min for 30min to obtain a mixed solution; placing the obtained mixed solution in a high-pressure kettle, heating to 120 ℃, keeping for 12 hours, cooling to room temperature to obtain a sample, and washing with ethanol and deionized water for three times respectively; washing with ethanol during the final centrifugation, dispersing the brown product in deionized water, storing in a refrigerator at 4 deg.C for later use, wherein the brown product is two-dimensional transition metal chalcogenide with chemical formula of Co2Fe1Mn1S4。
Example 3
Mixing 0.20mmol Co(NO3)2·6H2O、0.05mmolFe(NO3)3·6H2O and 0.15mmol Mn (NO)3)2Dissolving in 10mL of deionized water to obtain a cobalt-iron-manganese salt solution;
dissolving 0.1mmol of sodium nitrate and 50mmol of formamide in 10mL of deionized water to obtain a sodium nitrate solution containing formamide;
dissolving 0.0025mol of NaOH in 10mL of deionized water to obtain a sodium hydroxide solution;
simultaneously dropwise adding the cobalt-iron-manganese salt solution and the sodium hydroxide solution into the formamide-containing sodium nitrate solution at the dropwise adding speed of 2 mu L/s, and stirring in an oil bath at the temperature of 80 ℃ until the dropwise adding is finished; naturally cooling the system to room temperature, collecting the obtained sample through centrifugation, respectively washing the sample with ethanol and ultrapure water for three times, and further dialyzing (3kDa) to remove formamide to obtain the hydrotalcite nanosheet;
mixing the obtained 0.4mmol of hydrotalcite nanosheet serving as a precursor with 20mL of ethanol to obtain a dispersion liquid of the hydrotalcite nanosheet; mixing 0.8mmol thioacetamide with 20mL ethanol, and stirring at room temperature for 10min under the condition of 600r/min to obtain an ethanol solution of thioacetamide; then mixing the dispersion liquid of the hydrotalcite nano-sheets with an ethanol solution of thioacetamide, and stirring at the room temperature of 600r/min for 30min to obtain a mixed solution; placing the obtained mixed solution in a high-pressure kettle, heating to 120 ℃, keeping for 12 hours, cooling to room temperature to obtain a sample, and washing with ethanol and deionized water for three times respectively; washing with ethanol during the final centrifugation, dispersing the brown product in deionized water, storing in a refrigerator at 4 deg.C for later use, wherein the brown product is two-dimensional transition metal chalcogenide with chemical formula of Co2Fe0.5Mn1.5S6。
Example 4
0.40mmol Co (NO)3)2·6H2O、0.15mmolFe(NO3)3·6H2O and 0.05mmol Mn (NO)3)2Dissolving in 10mL of deionized water to obtain a cobalt-iron-manganese salt solution;
dissolving 0.1mmol of sodium nitrate and 50mmol of formamide in 10mL of deionized water to obtain a sodium nitrate solution containing formamide;
dissolving 0.0025mol of NaOH in 10mL of deionized water to obtain a sodium hydroxide solution;
simultaneously dropwise adding the cobalt-iron-manganese salt solution and the sodium hydroxide solution into the formamide-containing sodium nitrate solution at the dropwise adding speed of 2 mu L/s, and stirring in an oil bath at the temperature of 80 ℃ until the dropwise adding is finished; naturally cooling the system to room temperature, collecting the obtained sample through centrifugation, respectively washing the sample with ethanol and ultrapure water for three times, and further dialyzing (3kDa) to remove formamide to obtain the hydrotalcite nanosheet;
mixing the obtained 0.6mmol of hydrotalcite nanosheet serving as a precursor with 20mL of ethanol to obtain a dispersion liquid of the hydrotalcite nanosheet; mixing 0.12mmol thioacetamide with 20mL ethanol, and stirring at room temperature for 10min under the condition of 600r/min to obtain an ethanol solution of thioacetamide; then mixing the dispersion liquid of the hydrotalcite nano-sheets with an ethanol solution of thioacetamide, and stirring at the room temperature of 600r/min for 30min to obtain a mixed solution; placing the obtained mixed solution in a high-pressure kettle, heating to 120 ℃, keeping for 12 hours, cooling to room temperature to obtain a sample, and washing with ethanol and deionized water for three times respectively; washing with ethanol during the final centrifugation, dispersing the brown product in deionized water, storing in a refrigerator at 4 deg.C for later use, wherein the brown product is two-dimensional transition metal chalcogenide with chemical formula of Co2Fe0.75Mn0.25S6。
Example 5
0.60mmol Co (NO)3)2·6H2O、0.15mmolFe(NO3)3·6H2O and 0.05mmol Mn (NO)3)2Dissolving in 10mL of deionized water to obtain a cobalt-iron-manganese salt solution;
dissolving 0.1mmol of sodium nitrate and 50mmol of formamide in 10mL of deionized water to obtain a sodium nitrate solution containing formamide;
dissolving 0.0025mol of NaOH in 10mL of deionized water to obtain a sodium hydroxide solution;
simultaneously dropwise adding the cobalt-iron-manganese salt solution and the sodium hydroxide solution into the formamide-containing sodium nitrate solution at the dropwise adding speed of 2 mu L/s, and stirring in an oil bath at the temperature of 80 ℃ until the dropwise adding is finished; naturally cooling the system to room temperature, collecting the obtained sample through centrifugation, respectively washing the sample with ethanol and ultrapure water for three times, and further dialyzing (3kDa) to remove formamide to obtain the hydrotalcite nanosheet;
mixing the obtained 0.8mmol of hydrotalcite nanosheet serving as a precursor with 20mL of ethanol to obtain a dispersion liquid of the hydrotalcite nanosheet; mixing 0.16mmol thioacetamide with 20mL ethanol, and stirring at room temperature for 10min under the condition of 600r/min to obtain an ethanol solution of thioacetamide; then mixing the dispersion liquid of the hydrotalcite nano-sheets with an ethanol solution of thioacetamide, and stirring at the room temperature of 600r/min for 30min to obtain a mixed solution; placing the obtained mixed solution in a high-pressure kettle, heating to 120 ℃, keeping for 12 hours, cooling to room temperature to obtain a sample, and washing with ethanol and deionized water for three times respectively; washing with ethanol during the final centrifugation, dispersing the brown product in deionized water, storing in a refrigerator at 4 deg.C for later use, wherein the brown product is two-dimensional transition metal chalcogenide with chemical formula of Co3Fe0.75Mn0.25S8。
The product structure and performance test results are as follows:
co obtained in example 42Fe0.75Mn0.25S6The TEM image of (A) is shown in FIG. 1, and Co can be seen from FIG. 12Fe0.75Mn0.25S6Has a flaky structure, uniform distribution and uniform particle size.
Co obtained in example 42Fe0.75Mn0.25S6The AFM image of (A) is shown in FIG. 2, wherein the thickness of the nanosheet corresponding to the left side of FIG. 2 is shown on the right side, and Co can be seen from FIG. 22Fe0.75Mn0.25S6The sheet structure has a thickness of 1.1-1.3 nm.
As shown in fig. 3, the UV-vis patterns of the two-dimensional transition metal chalcogenides obtained in examples 1 to 5 are shown in fig. 3, and it can be seen from fig. 3 that the absorption at 808nm gradually decreases as the molar ratio of Fe to Mn decreases, and after the ratio of Fe to Mn is determined to be 3:1, the ratio of Co (Mn + Fe) is changed, and when Co (Mn + Fe) is 2, the absorption at 808nm of the obtained two-dimensional transition metal chalcogenides is the strongest.
The temperature change profile of the two-dimensional transition metal chalcogenide compound obtained in examples 1 to 5 within 10 minutes after 808nm laser irradiation is shown in FIG. 4, and it can be seen from FIG. 4 that Co2Fe0.75Mn0.25S6The temperature rise is strongest under 808nm laser irradiation, and the temperature is increased by 39.4 ℃, which shows that the two-dimensional transition metal chalcogenide prepared in example 4 has the best photo-thermal property.
Detection of Co at room temperature (298K) with TMB2Fe0.75Mn0.25S6The change in catalytic performance of (CFMS) is shown in FIG. 5, where A in FIG. 5 indicates the change in different concentrations of H2O2Absorption of lower TMB, B in FIG. 5 representing the catalytic Michaelis-Menten steady state kinetic calculations, C in FIG. 5 being a Lineweaver-Burk plot based on Panel B; as can be seen in FIG. 5, the absorption of TMB at 650nm increases gradually with time, indicating that a catalytic process can occur; obtaining the reaction rate V by fitting through a Mie equation and mapping through double reciprocalmax＝2.74×10-8Ms-1H required for the reaction2O2Amount K ofm＝0.46mM。
TMB was used at a heating temperature (318K) to detect Co2Fe0.75Mn0.25S6The catalytic performance is shown in FIG. 6, wherein A in FIG. 6 represents different concentrations of H under heating2O2Absorption of lower TMB, B in FIG. 6 representing the catalytic Michaelis-Menten steady state kinetic calculations, C in FIG. 6 being a Lineweaver-Burk plot based on Panel B; v is obtained by fitting through the Mie's equation and drawing through double reciprocalmax＝3.77×10-8Ms-1，KmWhen the concentration is 0.26mM, the reaction rate is obviously increased compared with the room temperature, and the required H2O2The amount of (a) is significantly reduced, further demonstrating that the heat generated by the material is capable of accelerating the process of the catalytic reaction.
Photothermal and catalytic performance was verified by cell experiments: with a mixture containing different concentrations of Co2Fe0.75Mn0.25S6DMEM medium (pH 6.5, H)2O20.1mM) for 12h, then irradiating for 8min by laser with 808nm, and then incubating for 12h, wherein the apoptosis level of selenide researched by the MTT method on cancer cells can cause about 92% of apoptosis at 30 mu g/mL, and the effect is obvious, as shown in figure 7.
Co2Fe0.75Mn0.25S6FIG. 8 shows the PI/CA staining pattern of the cell survival state of the tumor cells incubated at 30. mu.g/mL after 808nm laser irradiation, where 1 in FIG. 8 is a control group and 2 in FIG. 8 is pH 7.4 when Co is added2Fe0.75Mn0.25S6The survival rate of (1) in FIG. 8, when pH 3 is 6.5, Co is added2Fe0.75Mn0.25S6The survival rate of (1) in FIG. 8, when Co was added at pH 6.5 of 42Fe0.75Mn0.25S6The survival rate of the cells was 10 minutes after irradiation with a laser at 808 nm. The ratio of cell survival (green) to cell death (red) can be seen after PI/CA staining, corresponding to the results in fig. 7, where the synergy of photothermal therapy and tumor nanocatalysis caused the majority of cells to apoptosis.
Further study of Co2Fe0.75Mn0.25S6T of1MRI Performance, different concentrations of GSH (0mM, 2mM, 4mM and 10mM) and Co2Fe0.75Mn0.25S6Carrying out reaction; from FIG. 9, T at 0mM GSH1Weighted MR relaxation Rate (r)1Value) of only 3.28mM-1·s-1(ii) a Increase to 2mM and 10mM under GSH, r15.56 and 7.89mM respectively-1·s-1，r1And is significantly increased. As can be seen from fig. 9, the transition metal chalcogenide material obtained by the present invention has good magnetic resonance imaging performance.
The photoacoustic properties of the materials were evaluated by the MSOT imaging system: for Co2Fe0.75Mn0.25S6As shown in FIG. 10, the concentration of the sample increased (0 to 50. mu.g/mL)-1) Observing the strength of the PA signalRemarkably enhanced, and Co2Fe0.75Mn0.25S6The intensity of the photoacoustic signal of (2) is 3.25 times that of the photoacoustic signal of hydrotalcite, which shows that the PA performance is remarkable after sulfurization treatment, and the obtained transition metal chalcogenide material with enzyme characteristics has good photoacoustic imaging performance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A method for preparing a two-dimensional transition metal chalcogenide, comprising the steps of:
(1) mixing a cobalt-iron-manganese salt solution, a formamide-containing sodium nitrate solution and an alkaline solution, and carrying out coprecipitation to synthesize hydrotalcite nanosheets; the cobalt-iron-manganese salt solution is prepared by mixing cobalt salt, ferric salt, manganese salt and water, and the total concentration of the cobalt salt, the ferric salt and the manganese salt in the cobalt-iron-manganese salt solution is 20-40 mmol/L; the molar ratio of cobalt ions, iron ions and manganese ions in the cobalt-iron-manganese salt solution is (1-3): (0.25-0.75): (0.25 to 0.75);
(2) mixing the hydrotalcite nanosheets, thioacetamide and ethanol, and carrying out a displacement reaction to obtain a two-dimensional transition metal chalcogenide compound; the temperature of the displacement reaction is 120-150 ℃, and the time of the displacement reaction is 11-13 h.
2. The preparation method according to claim 1, wherein the concentration of formamide in the sodium nitrate solution containing formamide in step (1) is 4-6 mol/L, and the concentration of sodium nitrate is 9-12 mmol/L; the molar ratio of formamide to sodium nitrate is 400-600: 1.
3. The method according to claim 1 or 2, wherein the molar ratio of sodium nitrate in the formamide-containing sodium nitrate solution to the total amount of cobalt, iron and manganese salts in the ferrocobalmanganese salt solution in step (1) is 1: (2-4).
4. The method according to claim 1, wherein the alkaline solution in step (1) is a sodium hydroxide solution, an ammonia solution or a sodium carbonate solution.
5. The method according to claim 1 or 4, wherein the mixing in step (1) is performed by: dropwise adding the cobalt-iron-manganese salt solution and the alkaline solution into the formamide-containing sodium nitrate solution; the dropping speed of the cobalt-iron-manganese salt solution is 1-3 mu L/s; the dropping speed of the alkaline solution is 1-3 mu L/s.
6. The preparation method according to claim 1, wherein the co-precipitation in step (1) is carried out at a pH of 9-10, and the temperature of the co-precipitation is 75-85 ℃.
7. The two-dimensional transition metal chalcogenide compound prepared by the preparation method of any one of claims 1 to 6, wherein the chalcogenide compound is in a shape of a sheet and has a thickness of 1.1 to 1.3 nm.
8. Use of a two-dimensional transition metal chalcogenide as claimed in claim 7 for the preparation of a photoacoustic imaging contrast agent or a magnetic resonance imaging contrast agent.
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